US6800598B1 - Composition for use in a dishwashing machine - Google Patents

Composition for use in a dishwashing machine Download PDF

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Publication number
US6800598B1
US6800598B1 US09/744,726 US74472602A US6800598B1 US 6800598 B1 US6800598 B1 US 6800598B1 US 74472602 A US74472602 A US 74472602A US 6800598 B1 US6800598 B1 US 6800598B1
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Prior art keywords
particle
composition according
tablet
cavity
core
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US09/744,726
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Inventor
Guido Waeschenbach
Ralf Wiedemann
Enric Carbonell
Ludwig Hertling
Natascha Wolf Daschner
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Reckitt Benckiser Finish BV
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Reckitt Benckiser NV
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/42—Details
    • A47L15/44—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0082—Coated tablets

Definitions

  • the present invention relates to a composition for use in a dishwashing machine and a process for the use thereof.
  • washing programs essentially consist of the following basic steps: preliminary washing cycle, main cleaning cycle, one or more intermediate rinsing cycles, a clear rinsing cycle and drying.
  • the machine dishwashing agent for bringing about the cleaning action is added at the start of the main cleaning cycle
  • special agents are used, e.g. clear rinsing agents.
  • Clear rinsing agents are intended to ensure that when washing with water water droplets are not left behind on the washed articles which, after drying on, leave behind marks of substances dissolved/dispersed in the droplets.
  • an antibacterial activity e.g. cationic compounds or triclosan
  • silver protection agents e.g. benzotriazole
  • an odorous action fragments, perfume
  • bleaching action/disinfection chlorine bleaches
  • odour masking e.g. polyvinylpyrrolidone
  • anti-coating agents and enzymes for additional purposes (e.g. lipase for removing grease and fat deposits in the dishwasher).
  • modern dishwashers have no suitable charging systems for this purpose.
  • the aim of the present invention was consequently to combine in a single function the cleaning function and the function or functions of the substance or substances to be added during the clear rinsing cycle with a constant efficiency compared with the results obtainable with a separate charging or to permit the charging of substances other than the clear rinsing agent in the clear rinsing cycle.
  • DE-OS 20 65 153 and 20 07 413 disclose detergent blanks for use as detergents, in which it is inter alia provided that two components having a different functionality are combined.
  • the structure comprises an enveloping shell, which is e.g. formed from two shell halves comprising a cleaning agent, as well as a cavity enclosed by the shells and which contains additives such as softeners, brighteners, etc.
  • British patent 1 390 503 discloses a liquid detergent containing capsules, which are insoluble in the composition, but release their content if the composition is diluted with water. This objective is achieved in that the capsules are coated with a substance having a poor solubility in water solutions with high ionic strength, but becoming soluble if the ionic strength is reduced by dilution. It is pointed out that this procedure can be used to incorporate materials in the liquid cleaning agent, which are unstable in the latter or would produce an instability if added directly. It is also proposed that this procedure be used in order to delay the release of a specific substance. Reference is made to use in machine dishwashing agents and it is proposed for the encapsulation of tribromosalicylanilide in order to stabilize the latter. The encapsulated material is released within two minutes following the dilution of the cleaning agent with water, i.e. in the main cleaning cycle.
  • U.S. Pat. No. 4,082,678 describes a fabric conditioning product comprising a closed container containing a releasable agent, which is used to make water-insoluble or non-dispersible an inner container located in the container and which is normally water-soluble or water-dispersible, the inner container is containing a fabric conditioner.
  • the inner container is made from a substance, whose solubility in water is highly dependent on the ionic strength or the pH-value of the medium and the agent used for rendering the inner container insoluble is an agent for controlling the pH-value or ionic strength.
  • the pH-sensitive coating is a copolymer of the following monomers:
  • R is hydrogen or a methyl group
  • R 1 and R 2 in each case an alkyl group with 1 to 3 carbon atoms and x an integer from 1 to 4
  • the polymers described are insoluble at a pH-value of 9.5 or higher and are soluble at a pH-value of 8.5 or lower.
  • the aim of the invention described therein is that the substances only evolve their function during the rinsing cycle, protect the same up to the start thereof and then immediately release it. The use for dishwashing machines is not described.
  • Japanese patent KOKAI 50-77406 discloses a washing aid surrounded by a water-soluble envelope obtained by mixing polyvinyl acetal dialkyl aminoacetate and at least one organic acid, which is solid at ambient temperature.
  • This protective envelope serves to protect the washing aid during the main washing cycle and release it during rinsing cycles.
  • the described compound reacts to a change of the pH-value between the main washing cycle and the rinsing cycle.
  • the correspondingly enveloped particles are mixed with conventional pulverulent detergent.
  • the disadvantage of a possible partial dissolving of the protective envelope at the start of the washing cycle occurs.
  • European patent applications EP 284 191 A2 and 284 334 A2 disclose a water-soluble polymer film for the release of washing additives in the rinsing cycle of washing machines which, during the normal washing cycle, remains intact over a typical temperature range and rapidly dissolves in the rinsing cycle. It is pointed out that although the use of pH-sensitive coatings is known, said films are normally temperature-sensitive, so that they are not reliably stable during the different temperatures occurring in the washing cycle.
  • the solution proposed is a pH-dependent material (which undesirably also has a positive temperature-dependent dissolving behaviour), which is combined with a material having a negative temperature-dependent dissolving behaviour. This combination is intended to guarantee that the coatings do not dissolve at the high temperatures at the start of the washing cycle (particularly the very high temperatures occurring in American machines). No reference is made to a use for machine dishwashing agents.
  • European patent application EP 481 547 A1 discloses multilayer machine dishwashing agent tablets with a core, a separating layer surrounding the core and an outer layer for the sequential release of the ingredients of the different layers.
  • the aim of this tablet is to solve two different problems, namely 1) incompatible materials can be formulated together in a single tablet and released at different times in order to prevent mutual influencing and 2) compositions intended to evolve their functions at different times can be formulated in a single tablet.
  • PCT application WO 95/29982 discloses a machine dishwashing agent with a delayed release of a clear rinsing agent in the form of a nonionic surfactant, which forms together with an inorganic builder salt a core particle, which is provided with a wax-like envelope in order to ensure the delayed release
  • This envelope is a substance which does not melt at the operating temperatures encountered in the cleaning cycle, but which so gradually chemically disintegrates under alkaline pH-values that there is still left at the end of the main cleaning cycle an active clear rinsing agent quantity which is transferred into the clear rinsing cycle.
  • the envelope is rendered soluble by chemical saponification under alkaline pH-values, so that the time at which the clear rinsing substance is released from the core is a function both of the temperature and the length of the main cleaning cycle.
  • the patent application provides no teaching for the formulation of a product with which it is possible to release the clear rinsing agent only when the clear rinsing cycle arrives in all washing programs of any machine type.
  • the core ingredient active as the clear rinsing agent is a nonionic surfactant, which is absorbed on an inorganic builder salt. This leads to inferior clear rinsing results, particularly with respect to marks on glass.
  • the product is finally a mixture of granular detergent and granular clear rinsing agent particles.
  • the problem of the present invention is to provide a composition usable for most rinsing/washing programs of different dishwashing machine types and in each of these cases the substance or substances having only to evolve their action in the clear rinsing cycle are only released at the earliest at the start of the clear rinsing cycle.
  • the aim is to achieve this without restricting the choice of the cleaning agents used, the substance or substances used for the clear rinsing cycle and other ingredients of the composition.
  • this problem is solved with a solution characterized by a basic composition evolving its function essentially in the main cleaning cycle of the dishwashing machine; as well as at least one particle, with at least one core incorporating at least one substance, which evolves its function essentially in the clear rinsing cycle of the dishwashing machine and an envelope substantially completely surrounding the core or cores incorporating at least one compound, whose solubility increases with decreasing concentration of a specific compound in the surrounding medium.
  • Agents are provided so that at the start of the clear rinsing cycle a significant dissolving of the envelope or a significant detachment of the envelope from the core or cores is prevented.
  • the concentration of the specific compound in the local environment of the particle or particles is sufficiently high up to the start of the clear rinsing cycle so that up to this time there is no significant dissolving of the envelope or significant detachment of the envelope from the core or cores.
  • the particle or particles are coated with a substance which, substantially independently of the concentration of the specific compound in the surrounding medium, dissolves or separates during the main rinsing cycle of the dishwashing machine.
  • the basic composition is preferably in the form of a tablet.
  • An embodiment of the invention proposes that the at least one particle is so placed in or on the tablet that the concentration of the specific compound in the local environment of the particle or particles is sufficiently high up to the complete dissolving of the tablet to prevent a significant dissolving of the envelope or a significant detachment of the envelope from the core or cores.
  • the particle or all the particles are received in at least one tablet cavity completely surrounded by the basic composition.
  • the at least one cavity can receive one or more particles having alone or together essentially the same volume as the cavity.
  • the at least one cavity has a larger volume than the or all the particles received in the particular cavity.
  • the particle or particles are arranged loosely in the cavity interior.
  • the particle or particles are fixed, preferably by an adhesive, in the cavity interior.
  • the cavity is positioned substantially centrally in the tablet interior.
  • the invention also proposes that the tablet has a single, substantially spherical cavity.
  • the cavity receives a single, substantially spherical particle, whose external diameter is smaller than the internal diameter of the cavity.
  • the or all the particles are received in at least one cavity of the tablet, which is only partly surrounded by the basic composition.
  • the cavity is a depression in one of the surfaces of the tablet in which the particle or particles are at least partly received.
  • the particle is so received in the cavity or depression that it does not project over the surface or surfaces of the tablet.
  • a special embodiment of the invention proposes that the cavity or depression only contains a single particle, whose volume and shape in the vicinity of the cavity or depression substantially coincides with the volume and shape of the cavity or depression and substantially completely fills the same.
  • the cavity or depression is parallel to one of the surfaces to which it opens or in which it is located and has a substantially circular cross-sectional surface.
  • the invention also proposes that the cavity or depression opens to the surface or surfaces only to the extent that the particle or particles received therein cannot pass through the opening or openings of the cavity or depression.
  • the particle or particles prefferably be loosely arranged in the cavity or depression.
  • the particle or particles are fixed in the cavity or depression, preferably by an adhesive.
  • the basic composition incorporates at least one composition chosen from the group comprising machine dishwashing agent composition, water softener composition and washing intensifier composition.
  • the envelope incorporates at least one compound which for the concentration of the specific compound at the end of the main cleaning cycle of the dishwashing machine is not or is only slightly soluble and at the concentration of the specific compound in the clear rinsing cycle has such an adequate solubility that in the clear rinsing cycle it is so substantially dissolved or detached from the core or cores that an at least partial escape of the core material into the clear rinsing cycle medium is possible.
  • solubility of the compound increases with decreasing OH ⁇ ionic concentration and therefore decreasing pH-value in the surrounding medium.
  • the compound at a pH-value above 10 has little or no solubility and at a pH-value below 9 has an adequate solubility to ensure a substantially complete dissolving or detachment from the core or cores in the clear rinsing cycle, so that an at least partial escape of the core material into the clear rinsing cycle medium is possible.
  • the compound incorporates a polymer, preferably a pH-sensitive polymer, which comprises at least one repeat unit, which has at least one basic function, which is not part of the polymer backbone chain.
  • the polymer comprises at least one repeat unit, which is based on a compound selected from the group comprising vinyl alcohol derivatives, acrylates or alkyl acrylates, which have said basic function.
  • the polymer is a carbohydrate functionalized with said basic function.
  • the aforementioned basic function is preferably an amine and in particularly preferred form a secondary or tertiary amine.
  • repeat unit is based on a compound with the following formula III:
  • G is a linking group selected from —COO—, —OCO—, —CONH—, NHCO—, —NHCONH—, —NHCOO—, —OCONH—or —OCOO—
  • R 1 independently of one another, is hydrogen or an alkyl group with 1 to 3 carbon atoms
  • R 2 independently of one another, hydrogen or an alkyl group with 1 to 5 carbon atoms and x is an integer from 1 to 6.
  • the repeat unit is based on a compound with the following formula IV:
  • R 1 independently of one another, is hydrogen or an alkyl group with 1 to 3 carbon atoms
  • R 2 independently of one another, is hydrogen or an alkyl group with 1 to 5 carbon atoms and x is an integer from 1 to 6.
  • the basic function is an imine or a basic, aromatic N-containing group, preferably a pyridine group or an imidazole group.
  • the pH-sensitive polymer is derived from chitosan.
  • the invention finally proposes that the compound incorporates K-carrageenan.
  • the core or cores comprise at least one material selected from the group constituted by surfactants, antibacterial compositions, silver protection agents, fragrances, bleaches, disinfectants, odour masking agents, anti-coating agents and enzymes.
  • the core or at least part of the cores can be in the form of an encapsulated liquid, preferably in the form of a liquid contained in a gelatin capsule.
  • the core or at least part of the cores is in solid form.
  • the core or at least part of the cores has a melting point of more than 35° C., preferably between 55 and 70° C.
  • the invention also relates to a process for performing a dishwashing cycle in a dishwashing machine, where the composition according to the invention is added at an appropriate time during the prerinsing cycle or main cleaning cycle to the medium in the dishwashing machine.
  • the basic composition in the form of a tablet is not able, following its dissolving in the medium up to the end of the main cleaning cycle to make available a concentration of the specific compound in the medium which is sufficiently high in order to prevent a significant dissolving of the envelope and a significant detachment of the envelope from the core or cores, said adequate concentration of the specific compound is made available by adding a further composition such as e.g. a machine dishwashing agent composition, to the medium of the main cleaning cycle at an appropriate time.
  • a further composition such as e.g. a machine dishwashing agent composition
  • the composition according to the invention is characterized in that it gives excellent results both in the main cleaning cycle and in the clear rinsing cycle of a dishwashing machine.
  • the basic composition e.g. in the form of a tablet, is dissolved during the main cleaning cycle and can evolve its corresponding action (cleaning, water softening, washing intensification, etc.).
  • the particle according to the invention contains as the core material the substance or substances evolving their main function in the clear rinsing cycle of the dishwashing machine, e.g. clear rinsing agents.
  • Said substance or substances are protected by an envelope which, at the concentration of a specific compound, e.g. a specific ion such as OH— ion (and therefore at a specific pH-value) and the temperature of the main cleaning cycle are stable and do not or only insignificantly dissolve or separate. Only when said concentration drops significantly by dilution, i.e. at the start of the clear rinsing cycle, is the solubility of the enveloping material reduced so significantly that it rapidly dissolves or separates and that the active core material is released in the surrounding medium. It is important that the protection of the core material acts from the addition of the inventive composition to the water up to the start of the clear rinsing cycle, i.e. before the cleaning liquor reaches a sufficiently high concentration of the specific compound, as will be explained hereinafter.
  • a specific compound e.g. a specific ion such as OH— ion (and therefore at a specific pH-value) and the temperature of the main cleaning cycle are stable and do not or only
  • the particles with the envelope changing in the case of a modification of the concentration of the specific compound with respect to its solubility can be connected, e.g. enveloped with the basic composition by a granulation or similar process.
  • the particles can be surrounded by a further protective jacket, which e.g. comprises a water-soluble compound independent of the concentration of the specific compound.
  • FIG. 1 A typical pH-profile of a dishwashing machine.
  • FIG. 2 A first embodiment of the inventive composition in cross-section.
  • FIG. 3 A second embodiment of the inventive composition in cross-section.
  • FIG. 4 A third embodiment of the inventive composition in cross-section.
  • FIGS. 5a and b A fourth embodiment of the inventive composition in cross-section and in plan view.
  • FIG. 6 A fifth embodiment of the inventive composition in cross-section.
  • the ionic concentration or pH-profiles of the cleaning or rinsing medium in a dishwashing machine are dependent on the ingredients of the cleaning or rinsing agent used.
  • a typical pH-profile when using a conventional, basic machine dishwashing agent, e.g. CALGONIT® can be gathered from FIG. 1 (dishwashing machine used, BOSCH model SMS 3047).
  • the vertical, broken line subdivision indicates the duration of the following stages: prerinsing, main cleaning, intermediate rinsing, clear rinsing. It is clear that the pH-value during most of the main cleaning cycle is between 10 and 10.5. The pH-value drops following the pumping out of the washing liquor at the end of the main cleaning cycle and the inflow of fresh water to a value of 9 during intermediate rinsing and to between 8.5 and 9 during clear rinsing.
  • FIGS. 2 to 6 reveal possible embodiments of the composition according to the invention. In all cases the preferred tablet form is chosen for illustration.
  • FIG. 2 shows a tablet 1 comprising two half-tablets 2 and 3 , which can have the same or a different composition.
  • a tablet 1 comprising two half-tablets 2 and 3 , which can have the same or a different composition.
  • the two layers normally have a different composition and have different colours.
  • a single particle 6 comprising a core 8 and the envelope 9 and its external diameter is slightly smaller than the internal diameter of the tablet cavity.
  • particles 6 can also completely fill the complete tablet cavity and engage against the walls thereof. If the internal diameter of the cavity is slightly larger than the external diameter of the particles 6 , the particle can either be loosely received in the cavity or fixed therein by an adhesive applied.
  • the additional advantage arises that during the production process, e.g. the moulding of the individual components in successive stages, a deformation and possibly resulting damage to the core or cores and/or envelope of the core is reliably avoided and which could lead to a reduction in the protective action of the core envelope.
  • a deformation and possibly resulting damage to the core or cores and/or envelope of the core is reliably avoided and which could lead to a reduction in the protective action of the core envelope.
  • the surface of the particle is at the most only in partial direct contact with the surface of the basic tablet composition surrounding it. This can take place in the manner described in the application, but also in other ways achieving the sought objective. Examples are the loose arrangement of a smaller particle in a larger cavity, the fixing of a smaller particle in the larger cavity in such a way that no or only a partial contact occurs between the particle and the basic composition, the application of a protective coating to the core envelope according to the invention, etc.
  • the term “local environment”, as used in conjunction with a special embodiment of the particle according to the invention, designates the immediate environment around said particle.
  • the concentration of the specific compound in this local environment of the particle is the determining factor for its stability.
  • this concentration in the local environment of the particle at least up to a substantially complete dissolving of the tablet is determined by the molecule,passing into solution.
  • the origin of the “specific compound”, at least in the initial phase of the main cleaning process is a compound from the basic composition forming the tablet or is produced by it in the surrounding medium. In the most typical case with conventional, basic dishwashing agents, it is represented by OH ⁇ ions, whose concentration can be expressed as a pH-value.
  • a basic machine dishwashing agent composition is not used as the basic composition and instead e.g. a water softener composition or a washing intensifier composition
  • the protection of the particle envelope is possibly only ensured by an adequately high concentration of the specific compound in the local environment of the particle until the basic composition, e.g. the tablet has completely dissolved, namely in the cases where the basic composition is not able to provide a sufficiently high, corresponding concentration in the washing liquor.
  • the sufficiently high concentration in the washing liquor (and therefore also in the local environment of the particle or particles) is brought about by dissolving the machine dishwashing agent (or a further specific additive).
  • a conventional adhesive can be used for fixing the particle in the cavity and instead other compositions and agents can be employed which fulfil the same purpose, e.g. a mechanical fixing, such as e.g. adequate frictional engagement between tablet and particle at at least certain points or a plug connection between tablet and particle. It is also possible to use further compounds which melt or dissolve during the main cleaning cycle as fixing agents between the tablet and particle.
  • a mechanical fixing such as e.g. adequate frictional engagement between tablet and particle at at least certain points or a plug connection between tablet and particle.
  • further compounds which melt or dissolve during the main cleaning cycle as fixing agents between the tablet and particle.
  • the design of the cavity in the tablet or the particle received therein the most varied further geometrical shapes are possible, such as e.g. an ellipsoid, cylinder, etc.
  • the design and size of the cavity in the tablet and the particle received therein need not correspond to one another.
  • a cylindrical particle can e.g. be received in a spherical cavity. All possible further combinations
  • FIG. 3 shows a second embodiment of the inventive composition based on a conventional two-layer tablet 1 .
  • the upper half-tablet 3 is in two parts, which make available both an adequate cavity 5 for receiving the particle 6 and also an opening to the tablet side 11 .
  • the particle 6 is not completely surrounded by the basic composition of the tablet 1 , so that it is visible from the outside in the interior of the tablet 1 .
  • the particle can either be loosely received in the cavity 5 (provided that by a corresponding choice of the size of the particle 6 on the one hand and the size of the opening of the cavity 5 to the tablet side 11 on the other it is ensured that the particle or particles cannot pass through the opening in the cavity) or fixed in the interior of the cavity by corresponding agents, such as e.g. adhesives.
  • FIG. 4 shows a third possible embodiment. It is based on a unitary tablet 1 ′, i.e. a single layer 2 ′ with a unitary composition and colour. Using a suitable device a depression 4 ′ is formed in said layer 2 ′. Into the depression 4 ′ is placed the particle 6 ′, which in this case, because the depression to the side 11 ′ of the tablet 1 is only open to the extent that without fixing the particle could drop out of the depression, it is fixed in the depression with an adhesive 10 ′ or a fixing intermediate layer or mechanically (e.g. by frictional engagement). This principle can obviously be transferred to multilayer tablets.
  • the depression e.g. parallel to the side 11 ′ can have a substantially circular cross-section.
  • a random number of other cross-sections is possible, e.g. any random polygon.
  • the particle 6 ′ received in the depression 4 ′ can assume any random shape (independent of the shape of the depression 4 ′), such as e.g. an ellipsoid, cylinder, parallelepiped, etc.
  • FIG. 6 A further possible embodiment can be gathered from FIG. 6 .
  • This is essentially constructed like the embodiment of FIG. 4, i.e. a tablet. 1 ′ having a unitary structure, i.e. formed from a single layer 2 ′′ with a unitary composition and colour.
  • the particle 6 ′′ not only contains a single core (as in FIG. 4 ), but a plurality of cores 8 ′′ all embedded in an envelope 9 ′′.
  • the particle containing the substance or substances to be released in the clear rinsing cycle at least in the first phase of the main cleaning cycle, a local environment exists with an adequate concentration of the specific compound serving as a “trigger” for dissolving the envelope, i.e. in a phase where the concentration is still relatively low, i.e. briefly in a range in which increased solubility of the envelope would exist. This ensures that the envelope has an adequate stability up to the clear rinsing cycle.
  • the core of the particle or particles which is only to evolve its activity in the clear rinsing cycle, must incorporate at least one substance acting as a clear rinsing agent.
  • a slightly foaming, nonionic surfactant are e.g. fatty alcohol ethoxylates, fatty alcohol ethoxylate/propoxylates, ethoxylate/propoxylate polymers, such as e.g. the products of Synperonic® and Brij® range of ICI, the products from the Plurafac®, Pluronic® and Lutensol® range of BASF, the products from the Genapol® range of Clariant and the products from the Poly-tergent® range of Olin.
  • surfactants are alkyl polyglycosides, glucamides and alkyl pyrrolidones. It is obviously possible to use all other surfactants able to evolve the desired action as clear rinsing agents.
  • liquids or wax-like solids are liquids or wax-like solids.
  • a decisive part is not played by the aggregate state of the substance acting as the clear rinsing agent.
  • liquids can be made available prior to the application of the envelope as surfactant-containing capsules, such as e.g. gelatin capsules or can be brought into an envelopable state by other appropriate measures.
  • Solids can conventionally be directly provided with the envelope and the coating process may have to be matched to the corresponding substance.
  • melt mixtures have proved particularly advantageous and supply solid surfactant particles with a melting point above 35° C., preferably between approximately 55 and 70° C.
  • the 50:50 mixture A33 revealed an excellent stability and was easy to handle, particularly with a view to the subsequent coating process. All samples dissolved rapidly in water, so that in each case an optimum activity as a clear rinsing agent is ensured.
  • Bleach-containing, i.e. oxidizing dishwashing agent compositions significantly limit the use possibilities of fragrances usable in such compositions.
  • the controlled release of a fragrance in the clear rinsing cycle would allow a much greater flexibility when using fragrances.
  • a core for a corresponding inventive particle in that a mixture of 50 wt. % melted polyethylene glycol, e.g. PET 8000, 25 wt. % fragrance or fragrance composition and 25 wt. % diethyl phthalate are cooled in a mould in order to form an e.g. spherical particle weighing e.g. 0.75 g.
  • an inventive particle with a core or several cores incorporating an antibacterial composition in a tablet for use in a dishwasher would make available the possibility of simultaneously releasing two different compositions in the clear rinsing cycle, namely the antibacterial composition from the core or cores of the particle according to the invention and the clear rinsing agent from the conventional charging device of the dishwasher.
  • a corresponding core is produced in that a mixture of 100% melted benzalkonium chloride (Barquat® MS-100) is cooled in a mould in order to produce an e.g. spherical particle weighing e.g. 0.64 g.
  • a granular, lipolytic enzyme e.g. Lipolase® 100T (Novo)
  • a hard gelatin capsule with an e.g. rounded, cylindrical shape, e.g. of the type used for medicaments.
  • the material for enveloping the particle core or cores incorporates the substances evolving their function essentially in the clear rinsing cycle of the dishwasher has a solubility dependent on the concentration of a specific, selected ion.
  • the envelope is substantially insoluble in the main cleaning cycle and is made soluble and is detached from the particle if the concentration decreases during the intermediate rinsing cycle or cycles or the clear rinsing cycle.
  • concentration to be used during the screening of the polymers, are dependent on the formulation of the basic composition of the tablet into which the enveloped particle is to be incorporated.
  • the value for the highest concentration to be used for the screening process corresponds to the concentration of the selected ion encountered in the washing liquor, after the machine dishwashing agent has completely ok dissolved.
  • the lower value for the concentration should be fixed at 20 to 200 times below said higher value.
  • the materials to be investigated are dissolved in solvents in which they are readily soluble.
  • the solutions are spread over glass plates, then dried at ambient temperature until a constant weight occurs.
  • the glass plates are added at a controlled temperature to a beaker with test solution.
  • the solution is then stirred with a magnetic stirrer at a controlled stirring speed. After about 10 minutes the glass plates are removed from the beaker and dried at ambient temperature to constant weight. The results are expressed as weight loss (%).
  • the screening processes must be adapted to the composition of the machine dishwashing agent, because they exert a significant influence on the concentration or pH-profile in the dishwashing cycle.
  • the aim is in each case to check the degree of solubility of the corresponding materials under different states, namely high or low concentration or pH-value.
  • Stock solution 7.507 g glycine buffer (Merck 104169) 5.850 g NaCl topped up with water to 1000 ml pH 8 buffer 500 ml stock solution solution: 500 ml distilled H 2 O 1.23 g of 1 N NaOH pH 10 buffer 500 ml stock solution solution: 500 ml distilled H 2 O 32.6 g of 1 N NaOH.
  • Screening process 2 was performed with the following cleaning agent formulation in order to simulate the conditions in different stages of a dishwasher cycle. Concentrations of 4 to 5 g/l are of a conventional nature for the cleaning agent load in the washing cycle. Concentrations of approximately 20 to 40 mg/l are of a conventional nature for the clear rinsing cycle.
  • Cleaning agent formulation Ingredient wt. % Sodium perborate monohydrate 9.00 Sodium tripolyphosphate 48.00 Sodium carbonate 28.00 Polyethylene glycol 4.00 Polymer 1.50 TAED 3.00 Enzyme 1.50 Surfactant 3.50 Additive 1.50 Total 100.00
  • Screening process 3 is used for screening compounds, whose solubility changes as a function of the concentration of potassium ions.
  • the compounds discovered with such a screening process can be used if in the main cleaning cycle, as stated hereinbefore, there is a correspondingly high potassium ion concentration, which must be correspondingly reduced by dilution in the clear rinsing cycle.
  • Screening process 3 was performed with the following formulation to simulate corresponding conditions.
  • the polymer was produced in the conventional manner by bulk polymerization.
  • the screening test results were as follows:
  • Films of polymer 1 were produced from a 10% solution in isopropanol.
  • Films of polymer 1 were produced from a 10% solution in a mixture of water and 1 N HCl (17:1).
  • R 1 independently of one another, is hydrogen or an alkyl group with 1 to 3 carbon atoms
  • R 2 independently of one another, is hydrogen or an alkyl group with 1 to 5 carbon atoms and x is an integer from 1 to 6.
  • G is a linking group selected from —COO—, —OCO—, —CONH—, NHCO—, —NHCONH—, —NHCOO—, —OCONH—or —OCCOO—
  • R 1 independently of one another, is hydrogen or an alkyl group with 1 to 5 carbon atoms and x is an integer from 1 to 6, in exemplified manner polymers can be used having a repeat unit based on a compound of formula V:
  • polymer 2 e.g. a pH-sensitive polymer (“polymer 2”) with the repeat unit VI, which is commercially obtainable from SANKYO under the trade name AE®,
  • the above-described screening process 2 was also carried out with polymer 2. 15 g of polymer 2 and 5 g of Mowiol® 3-98 (Clariant) were dissolved in 200 ml of a water/ethanol/1 N HCl 12:8:1 mixture. Films were formed and tested in the manner described hereinbefore and the following results were obtained.
  • polymers having the desired characteristics or which can be easily modified in such a way that they are suitable for the purposes of the present invention are polymers of isomers or derivatives of pyridine. preferably copolymers with styrene or acrylonitrile of formulas VII and VIII, in which G is a substituent at a random point of the pyridine ring.
  • polymer 3 A polymer according to formula VIII, namely poly(4-vinylpyridine styrene) copolymer (Scientific Polymer Products, Inc.) “polymer 3” was tested according to screening process 2. 10 g of polymer 3 were dissolved in 230 ml of water/1 N HCl 6.25:1. The formation of the films and the performance of the tests were in the manner described hereinbefore and the following results were obtained:
  • polymers are (e.g. random) polymers derived from chitosan, based on the following monomer units IX and X
  • K-carrageenan Another ionic concentration-sensitive polymer is the polysaccharide K-carrageenan, which proved to be in screening process 3 (cf. example 2) a polymer whose solubility is dependent on the potassium ion concentration in the surrounding medium.
  • K-carrageenan is represented by the following formula XI:
  • polymer 4 This polymer, called “polymer 4” was tested according to screening process 3. 4 g of K-carrageenan were dissolved in 96 g of water. 10 g of Mowiol® 18-88 were dissolved in 90 g of water and both solutions were mixed. The resulting solution was used for forming films and performing tests in the manner described hereinbefore and the following results were obtained:
  • the different cores described in example 1 were used as a basis for the production of particles according to the invention. These cores were individually or in a plurality (FIG. 6) provided with an envelope in a device for the application of a film coating of the type known in the pharmaceutical industry (e.g. obtainable from Lödiger, Wegtlin, GS, t adesty and Driam).
  • a film coating of the type known in the pharmaceutical industry (e.g. obtainable from Lödiger, Weglin, GS, t adesty and Driam).
  • the core or cores prior to the application of said envelope the core or cores can be provided with a protective coating.
  • a protective coating e.g. cellulose, cellulose oderivatives, polyvinyl alcohol, polyvinyl alcohol derivatives and mixtures thereof.
  • a protective coating was used in all cases and use was made in preferred manner of a 10 wt. % aqueous solution of a polyvinyl alcohol, e.g. the polyvinyl alcohol Mowiol® 5-88 (Clariant).
  • the quantity of the protective coating applied can be varied by the expert as a function of the core composition and correspondingly adapted initial tests have revealed good results with 3 wt. % in case 1 a , 2 wt. % in case 1 b , 3 wt. % in case 1 c and 4 wt. % in case 1 d of the polymer (dry weight), i n each case based on the weight of the complete particle.
  • the concentration-sensitive envelope can be applied to the core or cores or the protective coating in any random quantity and thickness, provided that it is ensured that the envelope Is sufficiently rapidly dissolved or detached in the clear rinsing cycle to enable the substance contained therein to evolve its action.
  • the cores are applied 1 to 10 wt. %, preferably 4 to 8 wt. % of the concentration-sensitive enveloping material (dry weight), based on the total particle weight.
  • the size of the inventive particles should be such that they are not or at least not significantly discharged from the dishwasher during the pumping out processes following the main cleaning cycle or intermediate rinsing cycle.
  • a size of max diameter 1 cm is adequate. Larger or smaller dimensions can obviously be chosen, provided that the appropriate operation overall is ensured.
  • polymer 1 of example 3 was used as the envelope and applied as 10% solution of the polymer in 0.055 N aqueous HCl.
  • a typical two-layer dishwashing agent tablet suitable for receiving a clear rinsing agent particle in the cavity formed therein in accordance with the present invention can be produced by moulding the pulverulent ingredients in prior art machines and using operating parameters known from the prior art.
  • One possible tablet shape is a parallelepipedic tablet formed from two substantially equally thick layers and in the largest surface of each of these layers is formed a hemispherical recess, so that on joining together the two half-tablets a substantially spherical cavity is formed in the interior (cf. FIG. 2 ).
  • composition of the dishwashing agent tablet is based on commercially available products.
  • An exemplified composition can be gathered from table 2. It is obviously possible to use other compositions, particularly those optimized for supporting the compound surrounding the core (e.g. in the provision of alkalinity).
  • the clear rinsing agent particle produced according to examples 1a and 4 is placed in a hemispherical recess of the white or coloured half-tablet. Subsequently a fixing substance, e.g. an adhesive (e.g. polyethylene glycol, polyvinyl ether, polyvinyl alcohol, silicate, preferably melted PEG 4000) is applied to the corresponding half-tablet surface and optionally the clear rinsing agent particle and the second half-tablet (coloured or white) is pressed onto the first half-tablet with clear rinsing agent particle.
  • an adhesive e.g. polyethylene glycol, polyvinyl ether, polyvinyl alcohol, silicate, preferably melted PEG 4000
  • This example describes a test proving the transfer of the clear rinsing agent surfactant into the clear rinsing cycle using the tablet produced according to example 5.
  • the clear rinsing agent particles have an average surfactant or polyethylene glycol content of in each case approximately 0.37 g.
  • the average water quantity in the clear rinsing cycle is approximately 5 litres.
  • the expected maximum quantity of surfactant plus PEG in the clear rinsing cycle should therefore be 0.148 g/l when using one tablet per rinsing cycle.
  • Dishwashing agent tablet without clear rinsing agent particles temperature 65° C.
  • Dishwashing agent tablet with clear rinsing agent particles (example 6); temperature 65° C.
  • Dishwashing agent tablet with clear rinsing agent particles (example 6); temperature 55° C.
  • test described in this example is used for testing the composition according to the invention for effectiveness in the clear rinsing cycle.
  • the clear rinsing efficiency of separately added dishwashing agent and clear rinsing agent was investigated.
  • the dishwashing agent corresponded to the composition of the tablet according to the invention and a commercial clear rinsing agent was used.
  • a BOSCH SMS 3047 dishwasher was used. The water hardness was approximately 17 to 19° H. The temperature was 65° C.
  • the dishwasher was loaded with 20 glasses, 20 black porcelain plates and 20 cutlery items.
  • the dirtying of the dishwasher load was carried out in the following way. 50 g of minced meat (pork:beef 1:1) were roast with 2 g of fat. After reaching a slightly brownish colour, to the meat was added a gravy containing 100 ml of water, 1 g of gravy binder and 2.5 g of instant gravy.
  • This material was added to the dishwasher, the screen being closed by a plug in order to have the dirtying action in the machine up to the end of the washing program.
  • the dishwashing agent was fed in at the start of the clear rinsing cycle.
  • the dishwasher load was evaluated 10 minutes after the end of the dish rinsing cycle.
  • the mark or spot prevention efficiency is expressed as a percentage, 100% efficiency representing the maximum number of 228 points.
  • the results are given in table 4.

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  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
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DE19834182 1998-07-29
DE19834182 1998-07-29
PCT/TR1999/000034 WO2000006688A1 (fr) 1998-07-29 1999-07-29 Composition s'utilisant dans un lave-vaisselle

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US20030186828A1 (en) * 2000-09-28 2003-10-02 Thomas Holderbaum Recessed tablets and method for the production thereof
US20040147427A1 (en) * 2002-11-14 2004-07-29 The Procter & Gamble Company Rinse aid containing encapsulated glasscare active salt
US20040259749A1 (en) * 2003-05-23 2004-12-23 The Procter & Gamble Company Cleaning composition for use in a laundry or dishwashing machine
US20050126602A1 (en) * 2002-08-21 2005-06-16 Bsh Bosch Und Siemens Hausgerate, Gmbh Method for adapting a rinsing program in a dishwasher machine, and corresponding dishwasher machine
US20060180607A1 (en) * 2003-07-12 2006-08-17 Reckitt Benckiser N.V. Closure
GB2440796A (en) * 2006-08-10 2008-02-13 Mcbride Robert Ltd A detergent tablet
US20080110370A1 (en) * 2006-11-13 2008-05-15 Verrall Andrew P Water-soluble film
US20080176985A1 (en) * 2006-11-13 2008-07-24 Verrall Andrew P Water-soluble film
US20090029897A1 (en) * 2005-06-03 2009-01-29 Sandra Behr Detergent or Cleaning Agent
US8927026B2 (en) 2011-04-07 2015-01-06 The Procter & Gamble Company Shampoo compositions with increased deposition of polyacrylate microcapsules
US8980292B2 (en) 2011-04-07 2015-03-17 The Procter & Gamble Company Conditioner compositions with increased deposition of polyacrylate microcapsules
US9162085B2 (en) 2011-04-07 2015-10-20 The Procter & Gamble Company Personal cleansing compositions with increased deposition of polyacrylate microcapsules
US9186642B2 (en) 2010-04-28 2015-11-17 The Procter & Gamble Company Delivery particle
US9993793B2 (en) 2010-04-28 2018-06-12 The Procter & Gamble Company Delivery particles

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DE19856213A1 (de) * 1998-12-05 2000-06-08 Henkel Kgaa Punkttabelle
WO2001044433A1 (fr) * 1999-12-13 2001-06-21 Henkel Kommanditgesellschaft Auf Aktien Doses de lessive, produit vaisselle ou detergent a liberation controlee de la substance active
DE10035781A1 (de) * 1999-12-13 2001-07-12 Henkel Kgaa Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen mit kontrollierter Wirkstoff-Freisetzung
DE19963570A1 (de) 1999-12-29 2001-07-26 Reckitt Benckiser Nv Zusammensetzung zur Verwendung in einer Geschirrspülmaschine mit einer Basiszusammensetzung in Form einer Tablette
DE10032611A1 (de) * 2000-07-07 2002-01-24 Henkel Kgaa Maschinengeschirrspülmittel mit Zusatznutzen
US6521576B1 (en) 2000-09-08 2003-02-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Polycarboxylic acid containing three-in-one dishwashing composition
US6492312B1 (en) 2001-03-16 2002-12-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle
US6475977B1 (en) 2001-03-16 2002-11-05 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water soluble sachet with a dishwasher composition
ES2375224T3 (es) * 2001-05-14 2012-02-27 The Procter & Gamble Company Producto de limpieza.
DE10131722A1 (de) * 2001-06-30 2003-01-16 Henkel Kgaa Mehrphasen-Reinigungsmittel
DE10137925A1 (de) 2001-08-07 2003-02-20 Cognis Deutschland Gmbh Geminitenside und Polyethylenglycol
DE10257826A1 (de) * 2002-05-16 2003-11-27 Electrolux Home Prod Corp Geschirrspülmaschine und Verfahren zum Betreiben einer Geschirrspülmaschine bei Verwendung von einem Kombinationspräparat mit mehreren Wirkstoffen
GB0222964D0 (en) 2002-10-03 2002-11-13 Unilever Plc Polymeric film for water soluble package
ES2254862T3 (es) * 2003-06-24 2006-06-16 Unilever N.V. Composiciones detergentes.
DE10337814B4 (de) * 2003-08-14 2015-12-31 Budich International Gmbh Mehrphasige Wasch-, Putz-oder Körperpflegemitteltablette
EP1568762A1 (fr) * 2004-02-19 2005-08-31 Unilever N.V. Tablettes détergentes et leur procédé de fabrication
DE102004062704B4 (de) * 2004-12-21 2007-09-13 Henkel Kgaa Verfahren zur Herstellung eines portionierten Wasch- oder Reinigungsmittels

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US7205266B2 (en) * 2000-09-28 2007-04-17 Henkel Kgaa Laundry or dishwasher detergent tablet having at least one cavity
US20030186828A1 (en) * 2000-09-28 2003-10-02 Thomas Holderbaum Recessed tablets and method for the production thereof
US20050126602A1 (en) * 2002-08-21 2005-06-16 Bsh Bosch Und Siemens Hausgerate, Gmbh Method for adapting a rinsing program in a dishwasher machine, and corresponding dishwasher machine
US8419861B2 (en) 2002-08-21 2013-04-16 Bsh Bosch Und Siemens Hausgeraete Gmbh Method for adapting a rinsing program in a dishwasher machine, and corresponding dishwasher machine
US20040147427A1 (en) * 2002-11-14 2004-07-29 The Procter & Gamble Company Rinse aid containing encapsulated glasscare active salt
US20040259749A1 (en) * 2003-05-23 2004-12-23 The Procter & Gamble Company Cleaning composition for use in a laundry or dishwashing machine
US20060180607A1 (en) * 2003-07-12 2006-08-17 Reckitt Benckiser N.V. Closure
US20090029897A1 (en) * 2005-06-03 2009-01-29 Sandra Behr Detergent or Cleaning Agent
GB2440796A (en) * 2006-08-10 2008-02-13 Mcbride Robert Ltd A detergent tablet
US20100105821A1 (en) * 2006-11-13 2010-04-29 Monosol, Llc Water-Soluble Film
US20080176985A1 (en) * 2006-11-13 2008-07-24 Verrall Andrew P Water-soluble film
US8268914B2 (en) 2006-11-13 2012-09-18 Monosol, Llc Water-soluble film
US20080110370A1 (en) * 2006-11-13 2008-05-15 Verrall Andrew P Water-soluble film
US9186642B2 (en) 2010-04-28 2015-11-17 The Procter & Gamble Company Delivery particle
US9993793B2 (en) 2010-04-28 2018-06-12 The Procter & Gamble Company Delivery particles
US11096875B2 (en) 2010-04-28 2021-08-24 The Procter & Gamble Company Delivery particle
US8927026B2 (en) 2011-04-07 2015-01-06 The Procter & Gamble Company Shampoo compositions with increased deposition of polyacrylate microcapsules
US8980292B2 (en) 2011-04-07 2015-03-17 The Procter & Gamble Company Conditioner compositions with increased deposition of polyacrylate microcapsules
US9162085B2 (en) 2011-04-07 2015-10-20 The Procter & Gamble Company Personal cleansing compositions with increased deposition of polyacrylate microcapsules
US9561169B2 (en) 2011-04-07 2017-02-07 The Procter & Gamble Company Conditioner compositions with increased deposition of polyacrylate microcapsules
US10143632B2 (en) 2011-04-07 2018-12-04 The Procter And Gamble Company Shampoo compositions with increased deposition of polyacrylate microcapsules

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EP1100864A1 (fr) 2001-05-23
AU5768899A (en) 2000-02-21

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